Реакции N-алкил(арил)альд- и кетиминов с эфирами кислот фосфора. Монография
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1 1 1 ; 1) 31
3 . *
1
2 1 1 1 1 1) 31 ,
3 1 3 (36).
, ; 1) (35) (,DCl3, δ, 1. .): 1.29 (9),
,Me3), 2.30 . (1), NH), 2.38 c (3H, CMe), 3.67 (1H, PCH, 2JPH 20 0), 3.91 3.93 (6), MeOP, 3JPH 11 0). , ; 31 (,Cl4, δ,
1. .): 26.93.
4
(37) 1, 3 (38).
(RO)2P(O)H + MeCCl2CH=NBu-t 
(RO)2P(O)CHCCl2Me
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34 |
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NHBu-t |
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35 |
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35, R = Me ( ), ClCH2CH2 ( ) |
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(RO)2P(O)CHCCl2Me + 2,4,6-(NO2)3C6H2OH |
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(RO)2P(O)CHCCl2Me |
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NHBu-t |
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N+H Bu-t 2,4,6-(NO ) C H O- |
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2 3 |
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36 |
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36, R = Me ( ), ClCH2CH2 ( ) |
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MeO |
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Me |
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O |
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P(O)(OMe)CHCCl2Me |
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P(O)CHCCl2Me |
+ CF COOMe |
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-OCOF3 |
N+H2Bu-t |
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-O |
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N H2Bu-t |
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37 |
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, (3) (35)
(1) 1-(2) 1 1 (34)
1, , 1
1 . + 1 1
1 1 (4 ) -
1 (7 ). , (35) 1 1 1 1 1 1-
91
3 1 1 (39) |
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1- |
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MeONa/MeOH |
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(RO) P(O)CHC(Cl)Me |
2 |
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(RO)2P(O)CH |
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CMe2 |
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(RO)2P(O)CH |
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CMe2 |
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2 |
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Cl- |
N+HBu-t |
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NBu-t |
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NHBu-t |
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3a |
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4a |
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7a |
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MeONa/MeOH |
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(RO)2P(O)CHCCl2Me |
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(RO)2P(O)C=C(Cl)Me |
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NHBu-t |
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NHBu-t |
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35 |
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39 |
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1.2.5 1 , -4 4 3
N- -2-1-2-3 1 1
+ *,*-
(40) N- -2- 1 1
(2). + , 1 3 1, 1
– C-Cl, 1 -
N(III), 1, 3 1
1 – 1
1 . 4 2 1 1 , 2-
1 3 1 1 (2), - , N(III)
, - , 1
1 1 3 ( -
)- ,
1. 4 2 1 1
*,*- (40) N- -2- 1- 1 (2), 3 1 1 –
N- -2-( )1 (41).
, 1 1 1, :
1
1 1 – *,*- N- -2-
1 (42), 1 1 1 3 ( -
92
)- -1
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1 (41). |
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(R1O)2P(S)SH + Me2C(Cl)CH=NR2 |
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Me2C(Cl)CH=NHR2 (R1O)2P(S)S |
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40 |
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42 |
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Me C(Cl)CH=NHR2 |
Cl |
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2 |
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SP(S)(OR1)2 41
40, R1=Pr-i (a), Et ( ), n-Bu ( ); 41, R1 = i-Pr, R2 =t-Bu (a), R1=Et, R2=Bu-t ( ), R1=n-Bu, R2=Bu-t ( ), R1=Pr-i, R2 =Bn ( ), R1 = Et, R2=Bn ( )
N- -2-1-2- 1 (2) ,,l4
1 1 *,*-
(40), 1 0-5 ,. ( 1 -
1 20 , 1 2 1 24 . 4
2 . + 1 (41)
. , (41)
1 2 1 ; 1), 13,, 31 . )
2 N- - -2- ( )-2-1 1 (41 ). , ; 1) (CDCl3, δ,1. .): 1.18 (12H, Me2CHO, 3JHH 6.1 0), 1.52 (9H, CMe3), 1.85 (6), ,Me2), 4.62 . (2H, CHOP, 3JHH 6.1 0, 3JPH 12.1 0), 8.76 c (1H, CH=N), 14.25 . (1H, N+H). , ; 13, (,DCl3), δc, 1. .: 23.91 23.34 (OCHMe2, 3JPC 5.03 0), 27.56 c (CMe3), 28.34 (SCMe2, 3JPC 8.05 0), 52.09 (CS, 2JPC 4.02 0), 63.57 c (CMe3), 75.32 (Me2CHO, 2JPC 8.05 0), 177.45 (,H=N+). , ; 31 (CDCl3): δp 85.2 1. . ), %: , 44.89; H 8.50; P 8.18; S 16.88. C14H31ClNO2PS2. +, %: , 44.73; H 8.31; P 8.24; S 17.05.
) 1 , 1 1 (40) (2) CDCl3 -60 ,. 1 ;
1) 31 1
(42). + 2 N+H-1
δ 12 1. ., 1 δ 108 1. . ' ,
1
(43) Cl-1 3 1 – N- -
-2-1 1 Me2CHCH=NBu-t.
93
_
(i-PrO)2P(S)SH + Me2CHCH=NBu-t 
Me2CHCH=N+HBu-t (i-PrO)2P(S)S
43
1 CCl4 0 ,
15 1. * 1 – *,*- 2-1 1 (43).
' ; 1) (CDCl3, δ,
1. .): 1.31 (12), Me2CHO, 3JHH 6.1 0), 1.38 (6), Me2CH, 3JHH 7.0 0), 1.63 c (9H, CMe3), 3.63 (1H, CHMe2, 3JHH 7.0 0), 4.75
( 2H, CHOP, 3JHH 6.6 0), 8.51 (1H, CH=N+, 3JHH 9.0 0), 13.3
. (1), N+H). , ; 31 (,,l4, δ, 1. .): 107.8. |
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; 1) 31 1, |
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Me2CHCH[(i-PrO)2P(S)S]NHBu-t . /
1. N+H 1 (42) (43)
1, *,*- -
1 1 1.
, 1, 1 (40 ) 1 1 (2 ) ; 1) 31 1 δ 3.2 δ 81 1. ., 3 SH- 1
(40), , . .
(42). + 1 ;
(42) . *, (42) 1 1,
. 4,
1
. 4 (42)
, 2 1 1, -
1 (40), . +
1 1 1 *,*- -
2 11 (44) 1 (2),
1 – *,*- -S-1 (45) *,*-1-
[2-1-1-( -1)-2- ] (3 ).
94
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(i-PrO)2P(S)S- Et+3NH |
+ 2 + Me2C[SP(S)(OPr-i)2]CH=NBu-t |
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44 |
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47 |
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Et3N |
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(i-PrO)2P(S)S- t-BuNH3 + Me2C(Cl)CHO |
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46 |
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42a |
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H2O |
[t-BuNH |
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(i-PrO)2P(S)SH + Me2C(Cl)CH=NNBu-t |
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+ Me C(Cl)CHO + 40a] |
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40a |
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(MeO)3P |
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45 + (MeO)2P(O)CHNHBu-t |
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(i-PrO) |
P(S)SMe + (MeO) |
PHO + |
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C(Cl)Me2 |
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3a |
+ 1 1
, 3 (45) (3 ). ,
1 ; 1) 31 :
4 1 (40 ) 1
1 (45) 1,
(2) 1 1 (3 ) 1-
(1.2. ).
(i-PrO)2P(S)SH + (MeO)3P |
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(i-PrO)2P(S)SMe + (MeO)2PHO |
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45
(MeO)2PHO +Me2C(Cl)CH=NBu-t 
(MeO)2P(O)CHNBu-t
3a C(Cl)Me2
+2 1 ( 1:1, 2, -10 ,) 92% 1 *,*-
2 11 (44) 1 (2 ). +
2-( - )- 1 3 1 (47) 8% 1. ! 1 6 1, (42)
1 1 (41), 1
2 1 3 1 (47).
+N- - -2-
1-2- 1, . 61-62 , (40 11 . .). nD20=1.4285.
, ; 1) (CDCl3, , 1. .): 1.29 (9), ,3), 1.77 (6), ,3),
7.69(1), ,)=N).
95
$1 (42),
1 , 3 *,*-
-11 (46) Me2C(Cl)CHO. + 1,
1 1 (40 ) (2). 4 -1 2- 1-2- . + 1 3 1
(40 ) (46).
4 ; (46). , ; 1) (CDCl3, , 1. .): 1.47 (12), ,)2CH, 3J)) 6.1 0), 1.74 (9), CMe3), 4.80 (2), ,)*, 3JHH 6.1 0), 8.14 . (3), N+)).
, ; 1) 2-1-2-
. , ; 1) (CDCl3, δ, 1. .): 1.70 (3), ,)3, 3J))
7.0 0), 4.51 . (1), C),l, 3J)) 7.0 0, 3J)) 5.0 0), 9.71 (1), ,HO, 3J)) 5.0 0).
, 1 1 ( )
, 1 1
, (RO)2P(S)S- ArN+H3
[159].
, 1 - 1 1 (42) 1 (41)
1 1 (40) (2) 1 1
1 ; 1), 13, 31 .
+ ; 31 1
, 3 1 1
1 (41 ) 1 (42 ) CCl4. ,
1 1 1 1
, (41 )
1 1 (42 ) ( . 4).
+ ; 13,
, 3 (41 ) 1
(42 ) ( .5). , 1 1 1 1
1 1
1, – . *
1, 1
1 .
96
4
5 / 1 7 1 (40) (2) 1 1 1 ' 31
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(0,) |
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(1) |
(42) |
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(42), (%) |
(41) |
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(41), (%) |
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-60 |
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2 |
107,5 |
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100,00 |
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-50 |
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23 |
107,1 |
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100,00 |
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0,00 |
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-30 |
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54 |
105,1 |
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99,94 |
84,5 |
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0,06 |
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-20 |
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73 |
101,5 |
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99,92 |
84,6 |
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-10 |
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88 |
100,5 |
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97,73 |
84,6 |
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2,27 |
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99,2 |
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91,99 |
84,6 |
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8,01 |
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130 |
97,6 |
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75,94 |
84,9 |
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24,06 |
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143 |
95,9 |
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54,88 |
85,0 |
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45,12 |
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182 |
98,8 |
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20,33 |
85,2 |
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79,67 |
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98,8 |
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10,75 |
85,3 |
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89,25 |
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310 |
98,7 |
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4,34 |
85,4 |
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95,66 |
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420 |
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85,4 |
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100,00 |
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5 |
5 / 1 7 1 (40) (2) |
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1 1 1 ' 13$ |
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(42), (1) |
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(1) |
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(41), |
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(1) |
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-20 |
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118,2 |
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-15 |
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48 |
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128,1 |
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131,5 |
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177,5 |
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140,1 |
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178,0 |
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157,5 |
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178,7 |
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164,3 |
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178,6 |
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345 |
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178,5 |
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97 |
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+ 1 1 δ 158 1. . !
(40 ) (2 ) 1 -200,, 1
; 13, 1, 1
–
(41 ) 1 (42 ),
1 1 1 1
(41 ).
1 1 δ 7.7 1. . + ; 1) 1 -32 ,
1 1
1 δ 6.18 1. . 4 1 2
. 4 1,
, 1 ,
1 (42 ) δ 8.73 1. .
1.
) ; 1)
1 SH- (40 ). 4 -60 ,
δ 3.2 1. . ,
δ 12 1. ., 1
1 . , 1 1 1 1
2
(12.0 → 4.93 1. .), 1
1 3 (4.93 → 13.70 1. .),
(41 ). $ 1, 1
1 3 1 (42 )
(41 ):
(48) 1 (49)
- ;
1 1 3
( )- , SN1 1 1 1, 1 (49) 1
1 (41 ).
98
40 + 2 |
MeC(Cl)CH=N+HBu-t (i-PrO) P(S)S- |
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2 |
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42a |
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+ |
.. |
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Me2C(Cl)CH |
NHBu-t |
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Me C CH NHBu-t |
Cl |
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2 |
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SP(S)(OPr-i)2 |
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S |
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S |
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P(OPr-i)2 |
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48 |
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Me2C CH |
N +HBu-t |
Cl - |
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41a |
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SP(S)(OPr-i)2 |
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99
2. 8%$ # # 2 "9 ' + $29
, ; 1) Tesla BS – 567A
100 0 ( – ( ,, d- 1, d- , d-1, d- ). , ; 1), 31
AVANCE-600 (Bruker)
600.000 0 (1)), 242.88 0 (31 ) CDCl3 1 30°,. 5 1 1) ( ,, XC 31P – (H3PO4).
'
1 1 1 Bruker Smart Apex II CCD (lMoKa,
1 1, T = 20ºC). ,
1 1 1 1 11 SIR 1,
1 1 11 SHELXL-97. +
1 3 11 WinGX APEX2.
1 1 1 1
1 3 11 ORTEP3 PLATON.
M -1
DFS Thermo Electron Corporation (,<"). : 2-
. - 3 2 70 2+, 1 280º,, 1 50º,, 150º,, 200º,. $ 1 1 3
. * 1- -
1 11 «Xcalibur». . , 3
.
' (1) 1,
[182], 1 (2, 21, 34) - [183].
+ . 4
1 3 1 3
.
100